THE EXCESS THERMODYNAMIC PROPERTIES OF LIQUID (CH4+CD4)

The vapor pressure differences between a mixture of (CH4+CD4) and CH4 and between CD4 and CH4 were measured simultaneously with the CH4 vapor pressure: This was done at 29 temperatures between 97 and 122 K, and for six different mixtures, of compositions 0.150, 0.250, 0.375, 0.500, 0.625, and 0.750 mole fraction in CD4. These mixtures exhibit very small positive deviations from Raoult's law. Calculated excess Gibbs energies for equimolar mixtures were 0.60 J mol(-1) at 100 K and 0.42 J mol(-1) at 120 K. These values of G(E) are 2 to 3 orders of magnitude smaller than those typically found in binary mixtures of simple nonisotopic species. The molar excess enthalpy, calculated from the temperature dependence of G(E), is H-E(X = 0.5) = ( 1.5 +/- 0.2) J mol(-1). The experimental results were used to test three theoretical models: the vdW-1 fluid theory, 1cLJ perturbation theory, and the theory of isotope effects in mixtures. While the first two proved to be inadequate, the isotope effect theory agrees well with experiment.